Sulphonated aliphatic hydrocarbon



Patented Nov. 24, 1935 DERIVATIVES, USEFUL AS WETTING AND CLEANSINGAGENTS Frederick Baxter Downing, Carney: Point, N.

and Richard Gesse Clarkson, Wilmington. DeL, assignors to E. I. du Pontde Nemonrs 8: Co

pany, Wilmington, Del., a corporation of Delaware No Drawing- AnpucauonMay as, 1932,

Serial No; 814,290

15 Claims. (01. 260-156) This invention relates to chemical compounds,more particularly surface active substances and a process for themanufacture thereof.

As is well known, surface active compounds which possess cleaning,wetting and dispersing properties may be advantageously used in thevarious industries, for example, the textile and a leather industries,for a wide variety of purposes.

Thus, surface active compounds such as soaps, that is, the sodium saltsof the higher fatty acids, find a wide application in the laundering,dyeing and finishing of textiles. Soaps are characterized by thedisadvantage, however, that they are not soluble in acidic solutionssince-the alkali metal salts of the fatty acids are converted into theinsoluble fatty acids. Soaps are also precipitated in strongly alkalinesolutions. Furthermore, in hard water the alkali metal salts of fattyacids are precipitated as the insoluble alkaline earth metal salts, suchas those of calcium, magnesium and the like.

While other surface active substances have been prepared such as, forexample, the Turkey red oils (that is, the reaction products of castoroil with concentrated sulphuric acid at relatively low temperatures)which are more soluble than soaps in the presence of mineral acids andhard water, these substances are generally much less effectivedetergents than the soaps they are designed to replace.

It is an object of the present invention to produce new chemicalproductswhich are highly surface active, are water soluble, and possessgood wetting and detergent power even in relatively strongly alkalineoracidic solutions. A further object is the production of surface activecompounds having relatively soluble alkaline earth metal salts andwhich, therefore, are adapted foruse in hard water. A still furtherobject of the invention is the provision of a new and improved processfor producing the above described compounds. Another object is theproduction of these surface active compounds directly in a high state ofpurity. A further object is the production of compounds. of thecharacter described by a process involving a series of reactions whichproceed with great smoothness and almost theoretical I yields. Furtherobjects will appear hereinafter.

These objects are accomplished according to this invention wherebyproducts especially useful as detergent, wetting and dispersing agentsare produced by reacting unsaturated aliphatic hydrocarbons, containing8 or more carbon atoms and having a double bond at the end of the chain,

witha halogen sulphonlc acid in the presence of a halogenating catalystand treating the reaction product with a hydrolyzlng agent.

While the invention is subject to considerable variation andmodification in the manner of its practical application, particularly asregards the kind and proportions of the reactants and the exact methodof procedure, the following examples, in which the parts are by weight,will serve to illustrate some of the products falling within theinvention and how they may be prepared.

Example I Twenty parts 1-2-octadecylene obtained by dehydrating primaryn-octadecyl alcohol were dissolved in about 80 parts of carbontetrachloride. Approximately one-tenth part of pyrolusite was suspendedin the solution which was then cooled to about -5 G. Twelve parts ofchlorsulphonic acid were added slowly to the mixture with agitation, theresultant mixture being maintained at the above low temperature for aperiod of about two more hours. At the end of this time the temperaturewas allowed to rise to about 20-25 C. After standing at this temperaturefor 12-14 hours the liquid was poured into water, neutralized with 20%sodium hydroxide solution and about 6 parts of excess sodium hydroxideadded. The product was boiled for an hour to hydrolyze it and to removecarbon tetrachloride. The resultant solution was neutralized withsulphuric acid solution and then evaporated to a small volume. Theproduct was isolated by precipitating the inorganic salts with an excessof ethyl alcohol, filtering the alcohol solution and evaporating off thealcohol and water. The resultant product was a light brown 011, clearlysoluble in water, possessing high surface activity.

and characterized by unusual stability in combination with markedwetting, cleaning, and dispersing power even in strongly acid oralkaline solutions. The weight of product obtained in this way was 32.5parts.

Example I! more than 10% of hydrochloric acid and in solutionscontaining more than 10% of sodium hydroxide. In fact no tendencytowards instability was noticed in any alkaline, neutral or acidicaqueous solutions.

Example III The process of Example I was carried out in the presence ofabout one-tenth part of cuprous chloride instead of pyrolusite; Theyield of prodnot obtained by extraction with alcohol was about 25.5parts and its properties were similar to those of the substancesproduced as described in Examples I and II.

For comparison, the procedure described in Examples I, II and III wascarried out a number' of times without a catalyst, all other conditionsof operation and proportions of materials being the same. In markedcontrast with the reaction where a catalyst was used, it was observedthat after hydrolysis and neutralization of the hydrolyzed product withthe 10% sulphuric acid solution an oily liquid formed in the reaictionmixture. This oily substance was removed and the remaining liquidevaporated to a small volume and extracted with alcohol as described inExample I. The average yield-of product was about 23.0 parts. Thisproduct likewise was soluble in water and possessed good wetting,cleaning and dispersing powers. even in relatively strongly acidic oralkaline solutions. As will be apparent, however, the yield was not sohigh as that obtained from the reaction with a catalyst. Thus theincrease of yield obtained by the procedure of Example I, was about 41%.Actually the increase in yield wasprobably greater than this since theproducts obtained by the use of catalysts' were purer than thoseobtained without catalysts. This was shown by the fact that the aqueoussolutions of the products obtained with catalysts were perfectly clearwhile solutions of the products obtained without a catalyst were cloudy,the cloudiness probably indicating incomplete removal of the by-productoily material formed during the hydrolysis. Furthermore, theproducts'obtained from the reaction with a catalyst were moreeffective-wetting agents than the products obtained without-catalysts.

The unsaturated hydrocarbons employed in drocarbonsmay-be of thestraight or branched chain type.

Generally. speaking, the straight chain hydrocarbons having a singledouble bond at the end of the chain are preferred. Hydrocarbons of thiskind may be obtained in any suitable manner, 'for-- example, bydehydrating the primary alcohols obtained by hydrogenating fatty 'acidsor their esters, .e. g. those contained in palm oil, tallow, coconut oiland olive oil. Branched chain unsaturated hydrocarbons falling withinthe invention may likewise be obtained in any desirable manner, forexample, by, polymerizing relatively short chain olefines or bydehydrating synthetic higher alc0h91$ or mixtures tion.

thereof, e. g. those-produced by the hydrogenation of carbon oxidesunder elevated temperatures and pressures. Where branched chainhydrocarbonsare employed the better results are obtained the shorter theside chain.

In practicing the invention the halogen sulphonic acids preferablyemployed are chlorsulphonic acid and bromsulphonic acid. The proportionsof halogen sulphonic acid employed may vary within relatively widelimits dependinglargely upon the nature of the unsaturated hydrocarbontreated and the products desired. In general, it is preferable to employabout l-2 moles of halogen sulphonic acid for each double bond per moleof an unsaturated hydrocarbon. In certain cases, however, it may bedesirable to use larger or smaller proportions of the halogen sulphonicacid} it being understood that the desired reaction proceeds whether. asmall or large amount of sulphonic acid is employed.

' As indicated by the examples, the reaction of the halogen sulphonicacid with the unsaturated hydrocarbon is preferably effected in asuitable liquid medium, that is to say, a medium which is liquid at thetemperature of the reaction and is inert to the reactants and productsor does not affect, the reaction unfavorably. It may or may not be asolvent for the reactants and/or products. As examples of such mediamaybe mentioned carbon tetrachloride, ethylene-dichloride,trichlorethylene, tetrachlorethane, chloroform,

liquid sulphur dioxide, diethyl'ether, acetic anhydride, propionic acidand propionic'anhydride. Generally speaking, we prefer to employ solventor suspension media having a boiling point below about 100 C., andespecially desirable results have been obtained with carbontetrachloride.

The catalyst employed in accordance with.the invention may be anycatalyst favoring the halogenation of carbon compounds. By' halogenationis meant the action of a free halogen on a hydrocarbon whereby ahydrogen atom in the hydrocarbon is replaced bya halogen atom. Thecatalyst should preferably be soluble in the reaction mixture and,furthermore, should preferably be a compound which does not give rise tooxidation reactions. As examples of halogenating catalysts may bementioned antimony trioxide, antimonypentoxide, antimony trichloride,antimony pentachloride, antimony sulphate,

cuprous chloride, cupric oxide, cuprous oxide,

cupric sulphate, cupric acetate, manganese dioxide. pyrolusite,manganous sulphate, manganese oxide, ferric chloride. ferrous sulphate.

ferric sulphate, ferric o'xide, ferrous oxide, magnetite, vanadiumpentoxide, sodium vanadate, vanadyl sulphate, aluminum chloride,aluminum sulphate. cuprous iodide, sodium iodide, potassium iodide andfree iodine. It will berecognized that the results obtained with theforegong catalysts'may differ widely depending largely upon thespecificreactants and conditions of opera- We have found that the reactionproceeds very smoothly and the final products are exceptionally light incolor when unsaturated hydrocarbons of the character herein describedare reacted with chlorsulphonic acid in the presence of a chlorinatingcatalyst. Of the various chlorlnating catalysts with which we havepracticed this-preferred embodiment of the invention, the

results obtainedwith pyrolusite and iodine have been very-highlyadvantageous. The amount of catalyst employed may vary considerablydepending more or less upon the.

nature thereof and that of the reactants, but as a general ruledesirable results have been obtained by the addition of catalysts to thereaction mixture in proportions corresponding to about (Ll-5.0%- byweight of the reacting substances.

The time allowed for the reaction between the halogen sulphonic acid andthe unsaturated hydrocarbon to take place will depend largely upon thenature of the reactants, the catalysts and theconditions oi temperature.Under ordinary operating conditions it may vary from about 2 to 48hours. In practice, however, this reaction is ordinarily allowed toproceed until a sample of the product boiled with a hydrolyzlng agent issoluble in water.

While the temperature maintained in effecting the reaction with thehalogen sulphonic acid may vary within relatively wide limits, thetemperature employed should preferably be below that giving rise todecompositiomresiniflcation or polymerization of the reactants andproducts. In general, it is preferable to maintain the temperatures inthis. step of the process below about 50 C. and preferably within therange of about 10-+35 C. Ordinarily, higher temperatures tend to yielddarker product a The hydrolysis of the product resulting from thereaction of the halogen sulphonic acid and the unsaturated hydrocarbonmay be effected in a number 01 ways. Thus, water may be added until theacid concentration is relatively low and the resultant product boiled:or the sulphonated product may be neutralized and then heated with ahydrolyzing agent. In some cases it may be possible to effecthydrolysis, at least in part, by merely neutralizing the reactionproduct of the halogen sulphonic acid and unsaturated hydrocarbon withan aqueous alkaline reagent and then boiling the resultant product.Hydrolyzing agents which are suitable for the process. of the inventionare mineral acids, e. g. hydrochloric, sulphuric and the like, oralkaline reagents, e. g., alkali metal and alkaline earth metalhydroxides. In practice, we prefer to neutralize the sulphonated productwith an aqueous solution of an alkali metal hydroxide, preferably sodiumhydroxide, and heat ,the product with a further quantity of the alkalimetal hydroxide to eflect hydrolysis.

Thev amount of alkaline reagent employed for neutralization andhydrolysis of the sulphonation product should preferably correspond toat least one equivalent for every equivalent of halogen sulphonic acidused. Thus, if the reaction with the unsaturated hydrocarbon is carriedout by means ofone mole of chlorsulphonic acid.

neutralization and hydrolysis of the product may be effected with twomoles of sodium hydroxide.

- In general, it is preferable to use an excess of the alkaline reagentover the amount required for neutralization and hydrolysis.

The amount of water present during the hydrolysis,may vary widely, Verysatisfactory resuits are obtained, however, when the suphonated productis heated with solutions of mineral acids, alkali metal hydroxides orakaline earth metal hydroxides having concentrations of about 2-20%.

The temperature of the hydrolysis is subject to considerable variationbut should preferably be above 50 C. and below the temperature at whichthe reactants or products decompose. A temperature of about 100 C. isnormally satisfactory for carrying out the hydrolysis. If a solvent-orsuspension medium is used in the first step of the process, it ispreferably removed prior to or during hydrolysis by evaporation, steamdistillation or in any other suitable manner. .The time allowed'ior thehydrolysis is preferably determined by allowing the hydrolytic action toproceed until a sample of the product dissolves in water.

Products of some value as emulsifying agents may be obtained by reactingthe unsaturated aliphatic hydrocarbons with a halogen sulphonic acid inthe presence of a halogenating catalyst as above described, and thenmerely neutralizing the reaction product without hydrolyzing it. Theseintermediate products may also possess some wetting and detergent power,particularly it relatively short chain unsaturated hydrocarbons areemployed. In general, however, these products are insoluble or onlyslightly soluble in water.

The final products produced in accordance with the invention, on theother hand, are soluble in water. Furthermore, they are highly surfaceactive and possess excellent cleaning, wetting-and dispersingproperties. They are particularly valuable from a commercial standpointbecause of their stability in all kinds of acidic, alkaline and neutralaqueous media and are distinguished from any products previouslypreparedby their stability in strong acids and alkalies. Because ofthese characteristics our new products have an unusually wideapplication for industrial purposes. Since they may be used in acid,neutral or alkaline baths they are especially well adapted for thelaundering, dyeing, bleaching. carbonizing, mercerizing and finishing oftextiles. They are also well adapted for use as emulsifying andsolubilizing agents for water immiscible or only slightly misciblesolvents. They'may be employed assuch or in combination with watermiscible or immiscible alcohols, ketones or other additional materials,such as washing, cleansing, emulsifying and wetting agents, e. g.trisodium phosphate, Turkey red oils, soaps, aliphatic or aromaticsulphonic acids, such as alkylated naphthalene sulphonic acids, mineraloil sulphonic acids, sulphonated derivatives of abietic acid, sulphuricesters, saponin and aliphatic and aromatic acid amides, such as sodiumtaurocholate or sodium salts of analogous acid amides. When employedalone or in combination with other materials such as those mentionedabove they find wide application as pasting, cleansing, lathering,wetting or fulling agents in the dye, paper, textile and leatherindustries. The products of the invention may also be employed incombination with neutral, acid or basic salts which serve to increasetheir emulsifying, wetting and dispersing power, such as, for example,sodium sulphate. sodium chloride. sodium acetate. monodiand tri-sodiumphosphates, sodium carbonate, sodium b carbonate. and similar compoundsof the other alkali metals or of ammonium. Other additional materialswith which the products of the invention may be combined are bleachingand disinfectant agents such as persulphates, percarbonates andperborates: filling materials such as talc, marbe-dust, and starch:'adsorbing materials such as suitable clays, e. g. i'ullers' earth;protective colloids or dispersing agents such as gum tragacanth, gallacids and their derivatives, agar-agar, glue, metlwl cellulose, sulphitecellul"se lyes, sodium cellulose phthalate, calcium saccharate, albumin.sodium cellulose glycollate, gelatin, natural and artificial resins,derivatives of chloresterine; phosphatides. geloses, natural andartificial waxes, wool waxes, solvent and softening sulphonlc acidderivatives.

agents, organic bases and their salts such as alkylolamine saltsand-quaternary ammonium compounds, inorganic colloids, and alkalies; andscouring materials such as kieselguhr, powdered pumice, sulphur, flour,china-clay salt and the like. Desirable results for many purposes mayalso be obtained by employing the sulpho acids or salts thereof producedas herein described in combination with the various acyclic, monocyclic,or complex cyclic terpenes or derivatives thereof such as, for example,limonene, dipentene, terpinolene, terpinene, phellandrene, sylvestrene,.pinene, 'bornylene, sabine and their alcoholic, ketonic and aldehydicderivatives. It will be apparent, furthermore, our new products may becombined with a wide variety of other additional materials which possesswashing, cleansing,

emulsifying, wetting, dispersing, adsorbing, lathering. bleaching,germicidal and bactericidal powers. They may likewise have incorporatedtherewith artificial or natural perfuming substances, many of which inthemselves may possess detergent properties of some value.

In addition to the' advantages above enumerated the invention is furtheradvantageous in that it offers a large outlet for cheap raw materialsuch asoils and fats from natural sources and those obtainable in largequantities as byproducts from the textile, and leather industries, fromfish oils, and a large number of other sources. Moreover, many' of theseby-products have been of relatively little value or usefulnessheretoforebecause of the bad odor asso-' ciated therewith. By convertingthese raw materials to olefines for use in the present process odorceases to be a serious factor.

In the practical application of the products of the invention it hasbeen noted that as a general rule their wetting properties increase withthe number of carbon atoms in the unsaturated hydrocarbon employed up toabout 18 carbon atoms and thereafter decrease. It has also been notedthat the detergent properties of the product may vary within arelatively wide range depending largely upon the number of carbon atomstherein and the nature of the liquid in which they are employed. Thus,in soft water the detergent power increases with the number of carbonatoms in the starting material and the products prepared fromunsaturated hydrocarbons containing about 20-30 carbon atoms areespecially desirable. In hard water, on the other hand, productsprepared from unsaturated aliphatic hydrocarbons containing less than 20but more than about carbon atoms are preferred from the standpoint ofdetergent power, and those preparedfrom the unsaturated straight chainhydrocarbons containingabout 14 to 16 carbon atoms are particularlyadvantageous.

The chemical constitution of the products produced in accordance withthe invention has not been definitely determined and therefore we do notwish to be limited by any theory in this regard or in regard to themechanism of the reactions. In view of the enhanced wetting and.detergent power of these products, however, and their greater stabilityin strongly alkaline and acidic solutions than products previouslyprepared, it appears that they are most probably true As previouslypointed out, the products obtained by reaction of the unsaturatedhydrocarbon with chlorsulphonic acid in the presence of a chlorinatingcatalyst and then hydrolyzing are somewhat better than those obtained bya similar procedure without a catalyst.

the catalyst causes one reaction to occur to the exclusion orpractically to the exclusion of others. A probable course of thereactions occurring when chlorsulphonic acid is reacted upon a higheroleflne having a single double bond at the end of the chain in thepresence of a chlorinating catalyst may be illustrated by the followingequations, in which R represents a saturated hydrocarbon radicalcontaining at least six carbon atoms:

Sulionation SOaH Hydrolysis H H Hydrolysing H H agent )3 I. R- H R- -11where M is 9H, or a metallic radical such as -Na, -K, or thelike,depending upon the hydrolyzing agent used.

Another probable course of the reactions is as follows? Sulionation H nH H n. 'n-c=c-n+cisotn i iim OaH J1 Hydrolysis "dominated, or occurredpractically to the exclusion of the other, it would seem that Reaction Iwould be favored in view of the tendency of chlorine, in the presence ofa chlorinating catalyst, to attach itself to the alpha carbon atom.

If the radical R of the unsaturated hydrocarbon contains an unsaturatedbond, similar reactions 'would probablyoccur at this bond. As previouslyindicated, these products are usually less desirable for the purposes ofthe invention.

As many apparent and widely different embodiments of this invention maybe made without departing from the spirit thereof, it is to beunderstood that we do not limit ourselves to the foregoing examples ordescription except as indicated in the following claims.

We claim:

1. In a process for preparing surface active substances, the step whichcomprises V reacting an aliphatic unsaturated hydrocarbon, containing atleast 8 carbon atoms and having a double bond at the end of the chain,with a halogen sulphonic acid in the presence of a halogenatingcatalyst.

2. A process for preparing surface active substances, which comprisesreacting an aliphatic unsaturated hydrocarbon, containing at least 8carbon atoms and having a double bond at the end of the chain, with ahalogen sulphonic acid in the presence of a halogenating catalyst, andhydrolyzing the reaction product.

3. A process for preparing surface active substances, which comprisesreacting an aliphatic unsaturated hydrocarbon, containing at least 8carbon atoms and having a double bond at the end of the chain, withchlorsulphonic acid in the presence of a chlorinating catalyst, andtreating the reaction product with a hydrolyzing agent whereby thechlorine is removed from the hydrocarbon molecule.

4. A process for preparing surface active substances, which comprisesreacting an aliphatic unsaturated hydrocarbon, containing at least 8carbon atoms and having a double bond at the i end of the chain, withchlorsulphonic acid at a relatively low temperature, in the presence ofa chlorinating catalyst, and heating the resultant product with ahydrolyzing agent.

5. Aprocess for preparing surface active substances, which comprisesreacting an aliphatic unsaturated hydrocarbon, containing at least 8carbon atoms and having a double bond at the end of the chain, withchlorsulphonic acid in an inert liquid reaction medium, and in thepresence of a chlorinating catalyst, and treating the reaction productwith a hydrolyzing agent whereby .the chlorine is removed from thehydrocarbon molecule.

l 6. The process of producing a highly surface active substance, whichcomprises reacting an :aliphatic unsaturated hydrocarbon, containing atleast 8 carbon atoms and having a double bond at the end of the chain,with chlorsulphonic acid at a temperature within the range of about-10-+85 C., in an inert liquid reaction medium which is asolvent for theunsaturated hydro- I carbgn, in the presence of a chlorinating catalyst,

then removing the reaction medium, heating the remaining product with ahydrolyzing agent, neutralizing the resultant product and recovering theneutralized product.

7. The process of preparing surface active substances, which comprisesreacting a straight has chain unsaturated aliphatic hydrocarbon,containing at least 8 carbonatoms and having a single double bondat theend of the chain, with chlorsulphonic acid in proportionsmorrespondingto about 1 to 2 mols of chlorsulphonic acid per mole of unsaturatedhydrocarbon, in an inert solvent reaction medium boiling below about 100C.,, at a temperature within the range of -'-10-+35?' C., in thepresence of a,chlorinating catalyst, adding to the resultant productwater and about one equivalent of alkali metal hydroxide for everyequivalent ofchlorsulphonic acid used.

the proportions of water corresponding to an product.

aqueous solution of said alkali metal hydroxide having a concentrationof about 2-20%, he the product obtained to a temperature of about 100 C.to effect hydrolysis thereof and at the same time to remove the reactionmedium, neutralizing the hydrolyzed product with a mineral acid andrecovering the neutralized product substantially free from inorganicsalts.

8. In a process of preparing surface active substances, the step whichcomprises reacting an aliphatic unsaturated hydrocarbon containing 8 to18 carbon atoms, inclusive, and having a double bond at the end of thechain, with chlorsulphonic acid in the presence of a chlorinatingcatalyst.

9. In a process of preparing surface active substances, the step whichcomprises reacting an aliphatic unsaturated hydrocarbon containing 20 to30 carbon atoms, inclusive, and having a double bond at the end of thechain, with chlorsulphonic acid in the presence of a chlorinatingcatalyst.

10. In a process of preparing surface active substances. the step whichcomprises reacting branched chain aliphatic unsaturated hydrocarbonscontaining at least 8 carbon atoms and having a double bond at the endof the chain, with chlorsulphonic acid in the presence of a chlorinatingcatalyst.

11. In a process of preparing surface active substances, the step whichcomprises reacting an aliphatic unsaturated hydrocarbon containing atleast 8 carbon atoms and having a double bond at the end of the chain,with chlorsulphonic acid in the presence of a chlorinating catalystselected from the group consisting of inorganic oxides and salts ofantimony, copper, manganese,

iron, vanadium, aluminum, alkali metal iodides and free iodine.

12. The process of claim 8 in which the reaction product is subsequentlyheated with a hydrolyzing agent selected from the class consisting ofdilute acids and dilute alkalis under conditions adapted to replacechlorine atoms .by hydroxyl D 13. The process of claim 11 in which thereaction product is subsequently heated with a hydrolyzing agentselected from the class consisting of dilute acids and dilute'alkalisunder con.- ditions adapted to replace chlorine atoms by hydroxylgroups.

14. The process of clam 8 in which the aliphatic unsaturatedhydrocarbons correspond to the oleflnes obtainable by the dehydration-of alcohols from coconut oil. 1

15. The process which comprises reacting an aliphatic unsaturatedhydrocarbon containing at least eight carbon atoms and having a doublebond at the end of the chain with chlorsulphonic acid at'a temperaturebelow about 50 C.,- in an inert solvent for the unsaturated hydrocarbonin the presence of a chlorination catalyst, then removing'the solvent,heating the. remaining product with a hydrolyzing agent, neutralizingthe resultant product, and recovering the neutralized FREDERICK n.nownmo. RICHARD a. cmaxson.

